CN101637663A - Method for treating release gas in storage tank area - Google Patents
Method for treating release gas in storage tank area Download PDFInfo
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- CN101637663A CN101637663A CN200810012686A CN200810012686A CN101637663A CN 101637663 A CN101637663 A CN 101637663A CN 200810012686 A CN200810012686 A CN 200810012686A CN 200810012686 A CN200810012686 A CN 200810012686A CN 101637663 A CN101637663 A CN 101637663A
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Abstract
The invention relates to a method for treating discharged gas in a storage tank area. A condensation system and an adsorption system are arranged, and a storage tank is provided with a pressure control system; when the pressure in the storage tank is higher than ambient pressure, the storage tank discharges waste gas outwards; the discharged waste gas enters the condensation system and condensateis recovered; then the waste gas enters the adsorption system and is discharged after pollutants are further removed; when the pressure of the storage tank is lower than the ambient pressure, a discharged gas outlet of the storage tank is closed, and when the pressure in the storage tank is lower than a set value, a protective gas valve of the storage tank is opened, and protective gas is absorbedinto the storage tank; when the waste gas is not discharged in the storage tank area, the condensation system stops refrigeration, the protective gas enters and passes through the condensation systemand the adsorption system, and is circulated back to the storage tank to be taken as the storage tank protective gas or enter a low-pressure gas pipe network. The method has the characteristics of high hydrocarbon recovery rate, no secondary pollution, low energy consumption, high operation safety and the like, and can be used for treating discharged waste gas in an acidulous water storage tank area, an oil tank area and the like.
Description
Technical field
The present invention relates to a kind of method for treating release gas in storage tank area, particularly the improvement method of discharging waste gas such as the acid water storage tank district of industries such as oil refining, chemical industry, oil product tank field.
Background technology
Exhaust gas discharged such as the acid water storage tank district of industries such as oil refining, chemical industry, oil product tank field are important foul gas pollution sources, the pollutant such as volatile hydrocarbon, hydrogen sulfide, organic sulfur compound, ammonia that wherein contains higher concentration, if do not take effectively to administer method, serious pollution can be caused, a large amount of wastings of resources can be caused simultaneously.
The existing improvement method of this type of waste gas has several classes such as firing method, condensation method, bioanalysis, absorption method, chemical absorption method and combination method.Foul gas is handled and is selected which kind of treatment technology actually, can take all factors into consideration according to gas source, pollutant composition, concentration, tolerance, processing requirements, operation, security and technological adaptability.
Firing method can be handled various odorant pollutants, and oxidation deodorizing is thorough.This method can be divided into three types of direct burning, flame combustion method and catalytic combustions.Directly burning is applicable to high-concentration organic waste gas.The flame combustion method usually need be with foul smell and fuel mix, and ignition temperature is generally at 600～800 ℃, and stench and total hydrocarbon clearance are near 100%.Shortcoming is to need to consider the blast bound, and fuel consumption is big, and the trend that is replaced by catalytic combustion is arranged.Some refinery also utilizes the torch foul gas that directly burns usually.Catalytic combustion is under catalyst action, and organic pollution can be burnt under 200～300 ℃ of temperature, and stench and total hydrocarbon clearance can reach 99%.This method is simple to operate, efficient is high, has become a kind of important deodorization means, generally is suitable for handling low-concentration organic exhaust gas.Big and be in the tank deck foul gas in inflammable and explosive zone for hydrocarbon content height, sulfide concentration, should consider to prevent catalyst poisoning measure, explosion precaution and economy.
Condensation method and freezing generally are used to reclaim higher lighter hydrocarbons of boiling point or odorant pollutant.This method is usually united use with other method, as the condensation+adsorption technology of employing is arranged in the oil gas recovery; Chemical enterprise is handled the condensation+oxidation+adsorption technology that adopts when high concentration contains methyl disulfide (103 ℃ of boiling points), methyl mercaptan (6 ℃), methyl sulfide waste gas such as (37 ℃), methyl disulfide, methyl sulfide condensation are reclaimed, and the pollutant in the tail gas is further removed through oxidation and absorption.
Biological deodorization method utilizes attached to the microorganism metabolic processes on the filler, and pollutant is decomposed into CO
2, water, NO
3 -And SO
4 2-Etc. innoxious compound, have characteristics such as technology is simple, with low cost, be the technology of people's common concern.The prior biological technology is suitable for handling that source of the gas is stable, water miscible, biodegradable low concentration gas, is difficult to the foul gas of processing hydrocarbons content height, pollutant levels height, complicated component.
Absorption method is utilized the intrapore surface area of adsorbent absorption odorant, be a kind of traditional, still be in the deodorization technology of developing stage.Deodorization adsorbent commonly used has active carbon, amphoteric ion-exchange resin, activated alumina, silica gel, atlapulgite etc.Wherein, active carbon has higher voidage and specific area, can effectively adsorb boiling point and be higher than 40 ℃ malodor components.For H
2S (boiling point-60.4 ℃), CO
2(78.2 ℃), methyl mercaptan (6 ℃), ammonia (33.4 ℃), propane (42.1 ℃), propylene (47.7 ℃), hydrogen sulfide (60.2 ℃), ethane (88.5 ℃), ethene (103.7 ℃), butane (0.6 ℃), pentane (36.2 ℃), isopentane (28 ℃), trimethylamine low boiling odorants such as (3 ℃).Because the adsorption capacity of absorption method is lower, and no matter saturated adsorbent is that landfill or regeneration all produce secondary pollution, the replacing of adsorbent is trouble comparatively also, so absorption method generally is used to handle the foul gas of low concentration, or as the vent gas treatment of other method.
The adsorption and oxidation method is one of developing direction of absorption method.This method is a carrier with granular active carbon or fiber-reactive charcoal etc., by flooding alkali, having the noble metal of catalytic or the additives such as composite metal oxide of iron content, makes adsorption oxidation sweetening agent, is used to remove odorants such as hydrogen sulfide and organic sulfur.Deodorizing mechanism is that water vapour exists down H
2Odorant such as S, mercaptan and alkali reaction also are adsorbed on the desulfurizing agent, then under the metal catalytic effect with waste gas in oxygen reaction generate elemental sulfur, disulphide etc.This method is used in a plurality of fields such as tank deck foul gas processing.The problem that exists is that the adsorption reaction thermal discharge is big, when vulcanizing object height especially heat release violent, the influence safety in production; When steam and hydrocarbon content are high, easily wrap up desulfurizing agent, cause the desulfurizing agent effect to descend and lost efficacy; To form ferrous sulfide after the low or desulfurizing agent of air capacity is saturated, and because of the ferrous sulfide spontaneous combustion, have hidden peril of explosion, similarly explosion accident had taken place in some enterprise.
Absorption process can be divided into Physical Absorption method and chemical absorption method.The Physical Absorption method mainly is to be absorbent with water or diesel oil, removes water-soluble foul gas (as removing NH
3Or sulfide), but it is not up to standard to handle back gas, and employing can be used as preprocessing means seldom separately.Chemical absorption method can be divided into alkali absorb method, sour absorption process, chemical oxidization method, air catalytic oxidation method, metal ion catalysis oxidizing process etc., is widely used, and particularly the oxidizing process development is rapid, and selectable technology kind is many.
Though the most improvement that can be used for release gas in storage tank area of said method do not provide the suitable optimization process method in conjunction with the release gas in storage tank area characteristics.
Summary of the invention
The invention provides a kind of improvement method of release gas in storage tank area, characteristics such as the inventive method has hydrocarbon rate of recovery height, do not produce secondary pollution, processing safety height.
The exhaust in storage tank district and breathing process this area are called " breathing ", and the breathing that causes of fluctuating up and down of storage tank internal cause liquid level is commonly referred to as big breathing, and the breathing that causes because of the diurnal temperature fluctuation is commonly referred to as little breathing.In the large-scale storage tank district, in operation just often, big respiratory capacity generally can be controlled in the small range, therefore, and the main cause of discharging waste gas when little breathing is the normal running of storage tank district.Little breathing has certain rules, promptly is generally tank temperature rising in the daytime, outwards exhaust; Night, tank temperature descended, and is inwardly air-breathing; Form respiratory intermittently.Certainly, also have storage tank exhaust under the exceptional condition and air-breathing situation to take place.The present invention is directed to exhaust of storage tank district and air-breathing rule and characteristics, design following processing procedure.
Method for treating release gas in storage tank area of the present invention comprises following content, condenser system and adsorption system are set, storage tank is provided with control pressurer system, when tank inner pressure is higher than environmental pressure, the outside discharging waste gas of storage tank, discharging waste gas enters condenser system and reclaims condensate, enters then and discharges after adsorption system further removes pollutant; When tank inner pressure is lower than environmental pressure when low, close the storage tank discharging gas outlet, when tank inner pressure is lower than setting value, open storage tank protection air valve, protection gas is inhaled into storage tank; When the storage tank district did not efflux waste gas, condenser system stopped refrigeration, and protection gas enters condenser system and adsorption system, and the protection gas of process condenser system and adsorption system loops back storage tank and protects gas or enter the low pressure gas pipe network as storage tank.
In the inventive method, condenser system is provided with 2 grades or 3 grades, and first order control condensation temperature is 0～4 ℃, and the most of water vapor condensation that mainly will discharge in the gas is removed.According to requirement second level condensation and third level condensation are set to the volatile organic matter rate of recovery in the waste gas.Second level control condensation temperature-35～-20 ℃, about 60% volatile organic matter can reclaim in condensation.Third level control condensation temperature is-70 ℃～55 ℃, and the volatile organic matter of this moment about 80%～90% can reclaim in condensation, and remainder is removed in follow-up adsorption system, and Purge gas reaches the discharging standards discharging.
In the second level and third level condensation process, the water vapour in the waste gas can frosting in condenser, and sulfuration gas and ammonia in the waste gas also can generate the inorganic salts crystallization, and this will reduce the heat transfer efficiency of condenser system greatly, reduces the condensation recovering effect, increases energy consumption.Still contain more volatile component in the condensed waste gas, as hydrocarbon, hydrogen sulfide, ammonia, organic sulfur compound etc., can qualified discharge after the process absorption.
Adsorption system can be used various suitable adsorbents, the active carbon of preferred good adsorption performance.Because condensed EGT is lower, help improving the adsorption capacity of adsorbent, the potential safety hazard of having avoided the temperature rise in the adsorption process to bring simultaneously.Waste gas is generally 300～5000h by the volume space velocity of adsorbent
-1
The protection gas of storage tank can be any oxygen-free gas, preferred lower-cost nitrogen.Using the purpose of protection gas is the oxidation and spontaneous combustion that prevents the storage tank metal sulfide, and then causes security incidents such as burning even blast.
In the inventive method; in conjunction with storage tank exhaust and air-breathing rule trend; utilize the inspiratory duration section of storage tank night cooling; utilize protection gas to carry out the defrosting of condenser system and the regeneration of adsorption system; defrosting and regeneration can be according to the working conditions of condenser system and adsorption system; be provided with and carry out once every day, or per a couple of days carry out once, be generally and carried out in 1～5 day once getting final product.In some cases, storage tank also inspiratory phenomenon may occur in the daytime, but the general air-breathing in the daytime lasting time is shorter, should not carry out the defrosting of condenser system and the regenerative operation of adsorbent at storage tank inspiratory duration in the daytime.The specific operation process of defrosting and regeneration is as follows: elder generation is with the hydrops emptying of condenser system, replace with normal temperature protection gas then, to feed the protection gas lift temperature of condenser system after the displacement, and make the condensing zone internal temperature rise to 20～60 ℃ gradually, finish the defrosting of condenser; The protection gas that the process condensing zone is used to defrost further is warming up to 120～150 ℃ and enters adsorption system; adsorbent bed temperature raises and makes the material desorption of absorption; realize the regeneration of adsorbent, behind the regeneration ending with normal temperature protection gas to adsorbent bed lower the temperature standby.
The regeneration gas of discharging from adsorption system can have two whereabouts: 1. under pressure control as the additional gas in storage tank district; 2. by the pressure of protection source of the gas, import the low pressure gas pipe network.
The general normal pressure of storage tank uses, and therefore withstand voltage energy property is relatively poor, when in general tank inner pressure is lower than environmental pressure 1000～5000Pa, need opens the protection air valve and replenish protection gas in jar.Tank inner pressure is an environmental pressure～when being higher than environmental pressure 5000Pa, need open the gas extraction system valve to the exhaust treatment system exhaust.In order to prevent that contingency from taking place, and generally also need be provided with seal water system.
For administering acid water tank field emission gases, once charcoal absorption, diesel oil are absorbed, compress technologies such as gas pipe network, absorption-condensation-adsorption combined, condensation-adsorption combined and analyze.Active carbon absorption technology under the dense situation of acid water pot discharging gas and oil gas, exists that the adsorption process temperature rise is higher, regeneration is frequent, and absorption and regeneration are prone to problems such as active-carbon bed spontaneous combustion.The diesel oil absorption technique exists supply source problem, diesel oil length apart from transportation problem.The gas pipe network is advanced in compression, under the situation of aerobic, has piping corrosion, compression process blast and enters the possibility that nondestructive inspection gas burner explodes in discharging gas; In addition, compressor also be difficult to adapt to synchronously discharging tolerance from " zero " to 300m
3/ h arrives the discharge process of " zero " again.Absorption-condensation-adsorption combined can absorb depriving hydrogen sulphide, condensation and adsorption process by alkali lye and take off hydrocarbon, because very low by condensation discharging temperature degree, therefore, though charcoal adsorption process has temperature rise, operating temperature is controlled at below 40 ℃, does not have safety problem.The shortcoming of this technology is that flow process is longer.The present invention's hydrogen sulfide content in analyze grasping acid water tank field discharging gas is very low, hydrogen sulfide and ammonia will liquefy or generate crystallization at-60 ℃, and active carbon has under the situation of good adsorption properties recommendation employing condensation-adsorption technology processing acid water tank field emission gases to hydrogen sulfide and ammonia.
In the method for treating release gas in storage tank area of the present invention, make full use of the characteristics of storage tank district discharging waste gas,, designed suitable governance flowchart at the concrete condition of the polluter that is contained in the discharging waste gas.Simultaneously; the protection gas system that the defrosting of condenser system and the regeneration of sorbent system are supporting in the storage tank district, the flow process of simplification, the regeneration tail gas circulation is as storage tank protection gas or directly enter the low pressure gas pipe network; can not produce secondary pollution, simplify processing method yet.Compared with prior art, it is simple that the inventive method has flow process, and hydrocarbon rate of recovery height does not produce secondary pollution, handling safety, characteristics such as operation energy consumption is low.Be suitable for the purified treatment of tank field discharging gas such as acid water storage tank district, oil product tank field.
Description of drawings
Fig. 1 is a method for treating release gas in storage tank area schematic flow sheet of the present invention.
The specific embodiment
Further specify the inventive method below in conjunction with accompanying drawing.
As try hard to shown in 1, in the storage tank district exhaust period, by one-level condensing zone 3, B-grade condensation district 4 and three grades of condensing zones 5, all condensing zones and refrigeration unit 2 link storage tank district discharging waste gas 1 successively.At the one-level condensing zone, condensate liquid 9 is mainly water, can further handle.At secondary and three grades of condensing zones, condensate liquid 10 is mainly organic volatile, separate to reclaim in knockout drum 6, and the waste gas after condensation is reclaimed is by adsorption system 7, and the waste gas 8 that further adsorbs behind the pollutant wherein can qualified discharge.In the air-breathing period of storage tank district; condensing zone and storage tank block; hydrops in the emptying system; protection gas 11 enters condenser system and (can enter from the one-level condensing zone; preferably enter from the B-grade condensation district) and adsorption system replace; start protection hot-air heater 12 and regenerative heater 13 then; during protection gas process condensing zone; the frosting and the solid crystal of B-grade condensation district and three grades of condensing zones are removed; during protection gas process adsorption system; with the adsorbent desorption and regeneration, the regeneration gas 14 of discharge can loop back storage tank as protection gas, also can enter the low pressure gas pipe network.
Below by a specific embodiment explanation the solution of the present invention and effect.
Certain enterprise acid water storage tank district has 8 sewage storage tanks, carbon steel tank body, arch-roof tank.4 3000m
3Jar, 4 4500m
3Jar.Under the normal condition, the sour water amount is 160t/h, and when water was cut in the oil product tank field, sewage quantity can reach 200t/h.The time of staying of sewage in jar is generally more than 30 hours.
Acid water pot emission gases is formed as shown in table 1.
Table 1 acid water tank deck tidal air pollutant levels unit: μ L/L
| Pollutant | 2006.5.29 survey | 2006.6.2 survey |
| Hydrogen sulfide | ??＜0.01 | ??＜0.01 |
| Methyl mercaptan | ??0.07 | ??0.15 |
| Ethyl mercaptan | ??0.65 | ??＜0.01 |
| Methyl sulfide | ??1.11 | ??0.75 |
| Methyl disulfide | ??13.3 | ??7.25 |
| Benzene | ??2.29×10 3 | ??654 |
| Toluene | ??433 | ??137 |
| Ethylbenzene | ??2.19 | Do not detect |
| Paraxylene | ??1.17 | Do not detect |
| Meta-xylene | ??4.05 | Do not detect |
| Ortho-xylene | ??1.26 | Do not detect |
| Methane | ??744 | ??77.7 |
| Ethene | ??341 | ??25.7 |
| Ethane | ??1.54×10 3 | ??153 |
| Third is rare | ??2.70×10 3 | ??470 |
| Propane | ??5.86×10 4 | ??8.68×10 3 |
| Total hydrocarbon | ??579000 | ??181000 |
Set up in the acid water tank field under the situation of head space gas connection pipe network, calculate the maximum capacity in tank field, can be calculated as follows item by item:
Call out suction tolerance=200-160=40m
3/ h.
Little breathing capacity is by 8 total gas-phase space volumes of jar, day 15 ℃ of temperature rises (20 ℃ to 35 ℃), is the temperature interval that evenly raises at 6 o'clock to 14 o'clock, and calculating little breathing capacity is 140m
3/ h.
From the gas-entrained 80m that presses of the acid water of hydrogenation plant
3/ h value.
The maximum capacity in tank field is 260m
3/ h (normal temperature and pressure).
Ordinary circumstance, this enterprise's location daily temperature is changed to: 3 point～15 temperature raises, and 15 to 3 temperature reductions next day.
Gas emissions roughly changes with temperature Change.If the gas that does not have acid water to carry secretly, generally 16 to next day 3 whole tank fields should be in suction condition, do not have gas discharging; If the acid water entrained gas scale of construction is 80m
3/ h, the tank field should just enter suction condition after 21.
According to the inventive method, adopt flow process shown in Figure 1, by maximum capacity design condenser system and adsorption system, three grades of condensing zones are set, one-level condensing zone control temperature is 2 ℃, and B-grade condensation district control temperature is-30 ℃, and three grades are coagulated district's control temperature is-60 ℃, adsorbent is common commercially available active carbon, and design airspeed is 1000h
-1Through this treatment system, the total hydrocarbon rate of recovery arrives 88% (weight), and the every index of discharging tail gas all meets discharging standards.
Condensing zone defrosting and adsorbent reactivation are chosen at 22 to some next day 2, and defrosting control temperature is 50 ℃, and regeneration is controlled to be 130 ℃, and the regeneration tail gas part is as storage tank protection gas, and partial discharge is to the low pressure gas system.Once defrosted and regenerative operation in per 2 days, and can protect whole device under high efficiency, to operate.
Claims (10)
1, a kind of method for treating release gas in storage tank area, condenser system and adsorption system are set, storage tank is provided with control pressurer system, when tank inner pressure is higher than environmental pressure, the outside discharging waste gas of storage tank, discharging waste gas enters condenser system and reclaims condensate, enters then and discharges after adsorption system further removes pollutant; When tank inner pressure is lower than environmental pressure when low, close the storage tank discharging gas outlet, when tank inner pressure is lower than setting value, open storage tank protection air valve, protection gas is inhaled into storage tank; When the storage tank district did not efflux waste gas, condenser system stopped refrigeration, and protection gas enters condenser system and adsorption system, and the protection gas of process condenser system and adsorption system loops back storage tank and protects gas or enter the low pressure gas pipe network as storage tank.
2, in accordance with the method for claim 1, it is characterized in that described condenser system is provided with 2 grades, first order control condensation temperature is 0～4 ℃, second level control condensation temperature-35～-20 ℃.
3, in accordance with the method for claim 2, it is characterized in that it is-70 ℃～-55 ℃ that described condenser system is provided with 3 grades of third level control condensation temperature.
4, in accordance with the method for claim 1, it is characterized in that described storage tank protection gas is nitrogen.
5, in accordance with the method for claim 1, it is characterized in that described storage tank district is the inspiratory duration section of storage tank night cooling when not effluxing waste gas, utilize protection gas to carry out the defrosting of condenser system and the regeneration of adsorption system.
6, in accordance with the method for claim 5, it is characterized in that described defrosting and regeneration are provided with 1～5 day and carry out once.
7, in accordance with the method for claim 5, it is characterized in that described defrosting and regenerative process are: elder generation is with the hydrops emptying of condenser system, replace with normal temperature protection gas then, to feed the protection gas lift temperature of condenser system after the displacement, make the condensing zone internal temperature rise to 20～60 ℃ gradually, finish the defrosting of condenser; The protection gas that the process condensing zone is used to defrost further is warming up to 120～150 ℃ and enters adsorption system, and adsorbent bed temperature raises and makes the material desorption of absorption, realizes the regeneration of adsorbent.
8, in accordance with the method for claim 1, when it is characterized in that tank inner pressure is lower than environmental pressure 1000～5000Pa, open the protection air valve and in jar, replenish protection gas.
9, in accordance with the method for claim 1, it is characterized in that tank inner pressure is an environmental pressure～when being higher than environmental pressure 5000Pa, open the gas extraction system valve to the exhaust treatment system exhaust.
10, in accordance with the method for claim 1, it is characterized in that storage tank is provided with seal water system.
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| CN103566619A (en) * | 2013-10-29 | 2014-02-12 | 中国石油化工股份有限公司 | Method for recovering multi-component organic gas mixture |
| CN104014240A (en) * | 2014-05-20 | 2014-09-03 | 中国石油化工股份有限公司 | Processing method for malodorous gas of storage tank |
| CN104740889A (en) * | 2013-12-31 | 2015-07-01 | 财团法人工业技术研究院 | Gas treatment method and system |
| CN105584746A (en) * | 2014-11-18 | 2016-05-18 | 中国石油化工股份有限公司 | Recovery method for waste gas of refinery plant sewage tank |
| CN106693436A (en) * | 2015-11-13 | 2017-05-24 | 中国石化工程建设有限公司 | Tail gas treatment system for storage tank type material storage facilities |
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| US4010779A (en) * | 1975-03-20 | 1977-03-08 | Phillips Petroleum Company | Apparatus for recovery of vapor |
| CN2196098Y (en) * | 1994-04-12 | 1995-05-03 | 董衍安 | Lossless breathing device for oil tank |
| FR2827268B1 (en) * | 2001-07-12 | 2004-03-26 | Sellco Sa | FUEL STORAGE INSTALLATION IN A SERVICE STATION AND METHOD FOR FILLING A SERVICE STATION TANK |
| CN1994858A (en) * | 2006-11-24 | 2007-07-11 | 江苏工业学院 | Oil gas recovery method and device of fuel station |
| FR2909078B1 (en) * | 2006-11-24 | 2009-01-09 | Inst Francais Du Petrole | FUEL STORAGE FACILITY AND METHOD OF FILLING AND / OR EMPTYING THE TANKS OF THIS FACILITY |
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| CN103566619A (en) * | 2013-10-29 | 2014-02-12 | 中国石油化工股份有限公司 | Method for recovering multi-component organic gas mixture |
| CN104740889A (en) * | 2013-12-31 | 2015-07-01 | 财团法人工业技术研究院 | Gas treatment method and system |
| CN104014240A (en) * | 2014-05-20 | 2014-09-03 | 中国石油化工股份有限公司 | Processing method for malodorous gas of storage tank |
| CN105584746A (en) * | 2014-11-18 | 2016-05-18 | 中国石油化工股份有限公司 | Recovery method for waste gas of refinery plant sewage tank |
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| CN106693436A (en) * | 2015-11-13 | 2017-05-24 | 中国石化工程建设有限公司 | Tail gas treatment system for storage tank type material storage facilities |
| CN108114573A (en) * | 2016-11-29 | 2018-06-05 | 中国石油化工股份有限公司 | The collection and purification recovery system and method for a kind of tank area head space gas |
| CN109289227A (en) * | 2018-09-30 | 2019-02-01 | 上海峻岗环保科技有限公司 | A kind of organic matter recovery system and its recovery method |
| CN109351116A (en) * | 2018-12-06 | 2019-02-19 | 江苏科威环保技术有限公司 | Closed oil storage tank gas disposal process unit |
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